Hydroxy, halo and sulfato c2-4 carboxylic acid diesters of 3, 5 di-(hydroxymethyl) 4-loweralkyl aniline



United States Patent HYDRQXY, HALG AND SULFATO C CARBGX- YLlC ACIDDTEETEREl @lt 3,5 Dl-(HYDROXY- METHYL) 4-LGWERALKYL ANTLHNE WilhelmSchmidt-Nickels, Little York, N..l., assignor to General Aniline 3; Film(Importation, New York, N.Y., a corporation of Delaware No Drawing.Filed Dec. 31, 1962, Ser. No. 248,251

6 Claims. (Cl. 266-458) wherein R Z and R are selected from the groupconsisting of H, halogen, lower alkyl and lower alkoxy, R is selectedfrom the group consisting of H, halogen, lower alkyl, lower alkoxy, and

R is selected from the group consisting of H and lower alkyl, n has avalue of l to 3, Y is selected from the group consisting of NH and N0and X is selected from the group consisting of OH and ester-forminganions of a strong acid having a dissociation constant greater than 2.010- The invention also includes processes for producing compounds of theabove formula comprising reacting by heating one mole of a benzenecompound of the formula I R1- s R Xl-CHgCl wherein R Z and R areselected from the group consisting of H, halogen, lower alkyl and loweralkoxy, and R is selected from the group consisting of H, halogen, loweralkyl, lower alkoxy, and CH Cl with an amount of a compound of theformula M-OOC(CHR) OH, wherein M is alkali metal, R is selected from thegroup consisting of H and lower alkyl, and n has a value of l to 3,about molecularly equivalent to the number of --CH Cl groups in saidbenzene compound. To produce compounds wherein Y is NH the foregoingprocess is followed by the step of subjecting the product thereof totheaction of a reducing agent. To produce compounds of the inventionwherein X is other than OH, namely an ester radical, the product of theforegoing process is esterified by reaction with a strong acid having adissociation constant greater than 2.0

In the above formula, R, R R Z, R and R may be H or lower alkyl such asmethyl to butyl or isomers thereof. R R Z, R and R may be any halogenincluding F or I but preferably C1 or Br, or lower alkoXy ice Such asmethoxy to butoxy or isomers thereof. R may also be CH Cl and R may alsobe n has a value of 1 to 3.

X in the above formula represents OH or an esterforming anion as definedabove, the preferred anions being Cl and 080 1-1. Alternatively, X mayrepresent the anion of any other strong acid such as the anions ofhydrobromic, hydrofluoric, ioclic, phosphoric, phosphouic, phosphinic,organic sulfonic (sulfonyloxy), trichloroacetic, dichloroacetic,chloracetic, formic acids and the like.

The fundamental reaction for producing the compounds of this inventionrequires the use as precursor of a nitrobenzene containing at least onemeta-substituted chloromethyl group. Examples of such precursors aredisclosed in the prior art including US. 2,768,217. These and othersuitable precursors for use in the present invention may generally beprepared by reaction of an appropriately substituted or unsubstitutednitrobenzene compound with one or two moles of a chloromethylating agentsuch as bis-chloromethyl ether in the presence of sulfuric acid.Alternatively, chloromethylation of the nitrobenzene compound may becarried out by reaction with formaldehyde, zinc chloride and HCl.

The hydroxylic carboxylic acid salt of the formula MOOC(CHR) OI-l,wherein M is any alkali metal but preferably potassium or sodium, areknown compounds and/or are prepared in known manner. Thus, the alkalimetal salt of gamma-hydroxybutyric acid is prepared by treatment ofgamma-butyrolactone, or lower alkyl substituted derivatives thereoiQwithan aqueous alkali metal hydroxide solution. Similarly, the alkali metalsalt of ,B-hydroxypropionic acid is prepared by like treatment of e-proiolactone or its lower alkyl substituted derivatives. The alkali metalsalts of glycolic acid or lower alkyl substituted derivatives thereofmay also be employed for reaction with the chloromethylated nitrobenzeneprecursor.

The reaction between the chloromethylated nitrobenzene precursor and thehydroxylated carboxylic acid salt is preferably-carried out in a polarorganic solvent for the reactants. While methanol is preferred, othersuitable solvents may be employed as for example, ethanol, butanol,Cellosolves (lower alkyl and benzyl ethers of ethylene glycol),Carbitols (lower alkyl ethers of diethylene glycol), dioxane, acetone,methyl ethyl ketone, and the like. Reaction takes place at anytemperature from room temperature up to the boiling point of the mediumalthough elevated temperatures, for example at least 50 C., arepreferred to accelerate the reaction. The alkali metal chlorideby-product is precipitated during the reaction and readily removed as byfiltration after which the desired product may be recovered or isolatedif desired by evaporating the solvent from the medium.

The substituted nitrobenzene product of the process described in thepreceding paragraph may if desired then be subjected to the action of areducing agent to convert the nitro group to amino in any manner wellknown in the art. In such instances, it is preferred for economicreasons to dispense with a separation step and to instead treat thesubstituted nitrobenzene compound with the reducing agent in itsalcoholic or other polar organic solvent solution. This may for examplebe conveniently carried out by subjecting the filtrate containing thesubstituted nitrobenzene compound, after removal of the by-productalkali metal chloride, to reduction by the well known catalytichydrogenation process involving injection of molecular hydrogen,preferably under pressure, in the presence of a suitable catalyst suchasRaney nickel, platinum, palladium, and/ or their oxides, orcombinations thereof, preferably on a carrier such as charcoal or otherknown equivalents thereof.

Other methods of reduction may be employed including the use of the wellknown-reduction system containing a strong acid HX having adissociationconstant greater than 2.0 10 For example, treatment withconcentrated HCl or thionyl chloride yields the correspondingcompoundwherein X is Cl. such as sulfuric acid or pyridine-S0 complex yields thecorrespondingcompound wherein X is OSO H. Alternatively, otheresterifying acids of the type described above may be employed.

The products of this invention are surprisingly effective in theproduction of dyestuffs and other ohromophoric compounds reactive withtextile fibers, as described and claimed in my co-pendingapplicationSerial No. 248,243 filed on even date herewith. Thus, products wherein Yis NH and X is OH, as in Example 2 below, may be diazotized and coupledwith any known azo coupling component. Esterification of the resultingazo dyestuif to replace the terminal OH group by an ester group yields adyestuff reactive with textile fibers such as cotton under alkalineconditions with liberation of HX. Compounds wherein Y is NH and X is anester radical as defined above may be similarly diazotized and coupledWith an azo coupling component to yield a fiber-reactive azo dyestufi.

The following examples are only illustrative of the present inventionand are not to be regarded as limitative. All parts and proportionsreferred to herein and in the appended claims are by weight unlessotherwise indicated.

Example 1 A solution is prepared with 1900 parts by volume ethanol and93.6 parts by weight 2,6-bis-chloromethyll-nitrotoluene. Afterdissolving is completed at the boil, 128 parts by weight ofB-hydroxypropionic acid potassium salt are added and rinsed into thecharge by means of 100 parts by volume ethanol. chloride has separated,and is removed by filtration. All the alcohol is then evaporated on asteam bath leaving the reaction product of the structure:

HO-CH2CHFC O O-CH2 Example 2 A pressure shaker is charged with 200 partsby volume ethanol, 50 parts by Weight of the nitro compound of Example1, and 0.5 part by weight platinum oxide catalyst (Adams catalyst).Hydrogen is charged to'a pressure of 58 lbs. Within minutes the hydrogenpressure drops to lbs. Again hydrogen is added to a pressure of 58 lbs.The pressure drops to lbs. within 35 minutes and remain constant for 1hour indicating the completeness of the reduction. The catalyst isfiltered off and ethanol is removed by evaporation on a steam bath. Thereduction product'has the structure:

n0-o1n-om-c 0 0,-0112 After refluxing overnight potassium Reaction witha sulfating agent a The above product is diazotized, coupled with 1-(4-sulfophenyl)-3-methyl-5-pyrazolone, and esterified with concentrated HClto produce an azo dyestuif containing two fiber-reactive ClCH CH 'COO-CHgroups and yielding on cotton by the alkaline pad-cure method a brightyellow dyeing of good fastness properties. Similar results are obtainedif the above product is esterified with concentrated HCl prior todiazotization and coupling.

Example 3 A charge of 250 parts by volume ethanol, 11.7 parts by weight2,6-bis(chl onomethyl)-4-nitrotoluene and 11.8 parts by weightgamma-hydroxybutyric acid potassium salt is heated to reflux underagitation. Potassium chloride begins to precipitate from the solutioninitially formed. After stirring at reflux for 2 hours the solution isfiltered hot to remove the potassium chloride. The clear filtratecontains the compound of the structure:

Example 4 The filtrate from Example 3 is charged directly into apressure shaker. After addition of 0.3 g. platinum oxide catalyst (Adamscatalyst), hydrogen is charged to a pressure of 50 lbs. Within 40minutes the hydrogen pressure falls to 44 lbs. and then remainsconstant. After removal of the catalyst by filtration the ethanol isevaporated on a steam bath. Weight of remainder=20.3 parts by weight ofthe reduced product of Example 3.

Example 5 The entire product from Example 4 is introduced into parts byvolume conc. hydrochloric acid. The charge is then stirred at 72-75 C.for 2 /2 hours, by which time the reaction product has precipitated andis filtered off at room'temperature and sucked down sharply. It has thestructure:

A sample of this product is diazotized and coupled with1-(4-sulfophenyl)-3-methylpyrazolone-5. The resulting yellow dyestuff isapplied to cotton as described in Example 2. The cotton is dyed yellowWith similar fastness properties.

Example 6 A charge of 250 parts by volume methanol, 11.7 parts by weight2,6-bis(chloromethyl)-4-nitrotoluene and 22.9

parts by weight glycolic acid potassium salt is refluxed for 1 15 hours.

After allowing to cool to room temperature the potassium chloride formedin the reaction together with most of the excess glycolic acid potassiumsalt is re moved by filtration; Then the methanol is evaporated on asteambath. The remainder is dissolved in 200 parts by volume boilingethanol. On cooling to room temperature some retained glycolic acidpotassium salt crystallizes out. Itis filtered ofi. The filtratecontains the reaction product of the structure:

p The filtrate from Example 6 is charged into a pressure shaker. Afteraddition of 0.2 part by weight platinum oxide catalyst (Adams catalyst),hydrogen is charged to a pressure of 45 bs. Within minutes the hydrogenpressure falls to 32 lbs. and then remains at 32 lbs. for minutes. Afterremoval of the catalyst by filtration the ethanol is evaporated on asteam bath. The remaining product has the structure:

The above product, when diazotized, coupled, esterified and applied tocotton as described in Example 2, yields similar results.

Example 8 CHr- NHz 4.5 parts by weight of2,6-bis(fl-hydroxypropionatomethyl)-4-amino-toluene, prepared asdescribed in Example 2, are introduced at below 20 C. into 10 parts byvolume monohydrate (100% H 80 The charge is agitated at room temperaturefor 14 hours and drowned in ice to produce the above di-sulfato product.

The above product, when diazotized, coupled with Naphthol AS and appliedto cotton by the alkaline padcure method (padded on cotton from analkaline solution, dried, cured, e.g., at 150 C. and washed withdetergent to remove unreacted dyestulf) yields red dyeings of goodfastness properties.

This invention has been disclosed with respect to certain preferredembodiments and various modifications and variations thereof will becomeobvious to the person skilled in the art. It is to be understood thatsuch modifications and variations are to be included within the spiritand scope of this invention.

I claim:

1. A compound of the formula wherein Z is lower alkyl,

n is an integer of 1 to 3, and

X is selected from the group consisting of OH, halogen and sulfato.

2. A compound of the formula CH3 3. A compound of the formulaHO-CHz-CHrCHz-COO-OHz- CHg-OOO-CHz-C HrCHa-OH 4. A compound of theformula CHz-O O O-CHz-CHa-CHrCl 5. A compound of the formula(ll-CHz-CHg-ClIz-COO-CHF 6. A compound of the formula References Citedby the Examiner UNITED STATES PATENTS 8/54 Salvin et al. 857

OTHER REFERENCES LORRAINE A. WEINBERGER, Acting Primary Examiner.

LEON ZITVER, Examiner.

1. A COMPOUND OF THE FORMULA